EP0486070B1 - Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène - Google Patents

Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène Download PDF

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Publication number
EP0486070B1
EP0486070B1 EP91120674A EP91120674A EP0486070B1 EP 0486070 B1 EP0486070 B1 EP 0486070B1 EP 91120674 A EP91120674 A EP 91120674A EP 91120674 A EP91120674 A EP 91120674A EP 0486070 B1 EP0486070 B1 EP 0486070B1
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Prior art keywords
column
temperature
species
carrier gas
gas
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EP91120674A
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German (de)
English (en)
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EP0486070A1 (fr
Inventor
Christopher Huk-Shi Cheh
Ronald Ellard Massey
Otto Karl Kveton
Savtantar Kumar Sood
Samuel Hugh Hawthorne
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CHEH, CHRISTOPHER HUK-SHI
Hawthorne Samuel Hugh
Kveton Otto Karl
MASSEY, RONALD ELLARD
Sood Savtantar Kumar
Original Assignee
Cheh Christopher Huk-Shi
Hawthorne Samuel Hugh
Kveton Otto Karl
Massey Ronald Ellard
Sood Savtantar Kumar
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D59/00—Separation of different isotopes of the same chemical element
    • B01D59/22—Separation by extracting
    • B01D59/24—Separation by extracting by solvent extraction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D59/00—Separation of different isotopes of the same chemical element
    • B01D59/22—Separation by extracting
    • B01D59/26—Separation by extracting by sorption, i.e. absorption, adsorption, persorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B4/00—Hydrogen isotopes; Inorganic compounds thereof prepared by isotope exchange, e.g. NH3 + D2 → NH2D + HD
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G01N2030/3007—Control of physical parameters of the fluid carrier of temperature same temperature for whole column
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G01N2030/3023—Control of physical parameters of the fluid carrier of temperature using cryogenic fluids
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/26—Conditioning of the fluid carrier; Flow patterns
    • G01N30/28—Control of physical parameters of the fluid carrier
    • G01N30/30—Control of physical parameters of the fluid carrier of temperature
    • G01N2030/3084—Control of physical parameters of the fluid carrier of temperature ovens
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/16—Injection
    • G01N30/20—Injection using a sampling valve

Definitions

  • the present invention relates to a method for separating the isotopic species of hydrogen on a moderately large scale using low temperature gas chromatography.
  • the invention is addressed principally to those applications where a sufficient amount of material is not available to warrant a separation by cryogenic distillation.
  • the invention may be used to separate and store all six dimeric isotope species of hydrogen, i.e. H2, HD, HT, D2, DT, T2.
  • the capacity or throughput possible by use of the present method is much greater than that previously available without sacrificing the high separation efficiency obtainable by gas chromatography.
  • cryogenic distiliation has been known and used for the purpose of separating isotopic mixtures of hydrogen
  • this technique is only suitable for use on a large scale. Distillation suffers from the disadvatages of providing a low separation efficiency as well as requiring the retention of a fairly large inventory of material in the distillation system.
  • gas chromatography provides a high separation efficiency and leaves no inventory of desired material in the system, but generally, gas chromatography of hydrogen isotope mixtures has been utilized previously as an analytical tool.
  • Max Planck columns are packed with a pre-treated alumina powder. Separation times of 80 to 120 min were reported by them in Nuclear Tech/Fusion, 4, 687, 1983 for this system giving a throughput of 250 to 375 ml/h which may be written as 50 to 75 ml/h/1 cm column.
  • the present invention provides a method for chromatographically separating all six hydrogen isotope species at column throughputs of about 380 ml/h/1 cm column, or more than 5 times that of the Max Planck system.
  • column means a tubular structure usually made of metal such as copper or stainless steel which is packed with a material for effecting a separation of gaseous components which are caused to flow therethrough by means of a carrier gas.
  • Columns commonly used for gas chromatography are of a sufficient length that it is often inconvenient to deploy them in a linear fashion. Therefore, gas chromatography columns are frequently formed into spiral coils so that they may be conveniently stored and used, however, linear columns are within the scope of the invention.
  • Alumina used for chromatography is a synthetic polymeric material having a highly active surface.
  • the activity of the alumina may be reduced by moisture and by the incorporation of trace amounts of iron or other metals into the alumina crystal structure.
  • Highly activated alumina can completely adsorb hydrogen at sub-ambient temperatures.
  • chromatography on molecular sieves proceeds on the basis of molecular size.
  • Molecular sieves are synthetic material usually prepared from sodium or calcium aluminum silicates and are commercially available in beads having pore sizes in the range of 3 to 10 angstroms. The pores in each bead form a network of interconnecting tunnels so that small molecules entering the pores may pass through the network more readily than larger molecules.
  • a separation of molecular species is accomplished by a sieving effect whereby smaller molecules pass through the sieve faster than larger molecules. Elution is usaually in order of increaseing molecular size.
  • Molecular sieves are used commonly in chromatographic applications to separate gases such as helium, hydrogen, argon, oxygen, nitrogen, methane and carbon monoxide. Water, carbon dioxide and hydrocarbons are highly retained by molecular sieves. Oxygen and nitrogen are completely retained by molecular sieves at -50°C and hydrogen is retained below -180°C.
  • the carrier gas for conducting the gas chromatographic separation of hydrogen isotope species on molecular sieves must not interact strongly with the column packing so as to adversely modify the retention of the analytes. This rules out argon which absorbs very strongly on molecular sieves at temperatures below -20°C, however helium or neon do not interact strongly with molecular sieves at temperatures as low as -180°C and therefore, may be used.
  • a suitable carrier gas must also have a sufficiently high diffusion rate through the column packing so that the pressure drop across the column is low. This feature reduces the likelihood of leaks forming. Separation of the carrier gas from the separated components must be readily achievable, and the carrier gas must be compatible with the detector means used to monitor the effluent from the column.
  • helium is the preferred carrier gas for use in the invention.
  • the chromatographic systems described in the literature use narrow bore analytical columns (2 mm ID) which provide optimum efficiency but minimum capacity ( ⁇ 1 mL. chromatographed).
  • the ability of a column to separate components of a mixture is a measure of column efficiency.
  • the gas components must have different affinities for the packing material and sufficient surface area of the packing material must be available to ensure that the gaseous components equilibrate with the surface all the way down the column.
  • equilibrium conditions eventually are not satisfied and the column loses efficiency.
  • the point at which a significant loss in efficiency is detected is defined as the column capacity.
  • the loss in column efficiency is manifested in band broadening, decreasing retention times, and changing peak shape. Column capacity depends on the choice of column packing material and the size of the chromatographic bed.
  • a gas chromatography system includes a carrier gas supply, gas chromatography columns, a temperature controlled container for the columns, flow switching, gas detectors, and carrier gas/hydrogen isotope separation facilities.
  • the GC column was conditioned before it was used to separate hydrogen isotopes and re-conditioned every three to four months. The conditioning and normal operation of the column are discussed below.
  • FIG. 2 A more detailed schematic diagram of the equipment used is shown in Figure 2.
  • the system can be divided into five parts, namely, sample preparation, gas supply, column container, gas detection and data recording systems.
  • hydrogen isotope gas mixtures were prepared in a 1.7 L aluminum cylinder 11.
  • the cylinder 11 was fitted with two entry ports 12 and 13 and a pressure gauge 14. One of the ports 13 was connected to a septum 15 and the other port 12 attached to either a vacuum pump or a high pressure gas cylinder 16.
  • the sample cylinder 11 was evacuated to at least 10 ⁇ 2 torr. Pure gas components were then introduced into the cylinder by syringes through the septum 15. After addition of appropriate amount of gas, the cylinder 11 was pressurized with either deuterium or hydrogen from the cylinder 16 up to 200 psig (1.38 MPa).
  • the cylinder 11 was connected to a six-way valve 20 to fill the sample loop 21 at the desired pressure to be injected to the gas chromatographic column.
  • the sample mixture comprised approximately 50% H2 and 50% D2 with 2.5 to 5.0 ⁇ Ci/L T2 with catalytic equilibration within the sample cylinder in the presence of a metal catalyst, so that all six dimeric isotope species were obtained.
  • He, N2, and P10 (Ar and CH4 mixture) gases are provided by high pressure gas cylinder.
  • N2 was used to pressurize the liquid nitrogen container 25
  • P10 gas was used in the flow proportional counting detector 27.
  • FIG. 3 shows the valve 20 position when the sample loop 21 was being filled with gas samples from the sample cylinder 11. In this position, the sample loop 21 was evacuated by closing the valve connected to the sample cylinder 11 and opening the valve to the vacuum pump. Then, the valve to the vacuum pump was closed and the valve connected to the sample cylinder 11 was opened to pressurize the sample loop 21 with the hydrogen isotope sample to the desired pressure.
  • the apparatus illustrated in Figures 1 to 4 was designed as a multipurpose apparatus, and not specifically for the purposes of the present invention.
  • it was designed to evaluate a method of separating one or more isotopes of hydrogen from a mixture of such isotopes involving "peak-cutting" all enriched isotope-containing fraction from a first column for further concentration in a second column, that method being described in detail in EP-A-0245936 and from which the present application is divided.
  • peak-cutting two separate chromatography columns are provided, both mounted in the container 40, and connected in series by the six-way valve 30.
  • valve 30 For the purposes of the present invention, however, only a single column was used, and the output from that column was passed directly to the isotope detector/collection systems by the valve 30, and not via a second column. Thus the positions of the valve 30 shown in Figure 3c does not apply to the present process, whilst in Figures 3a and 3b the outlet port from valve 30 was connected direct to the detectors rather than to a second column.
  • the column was placed in a vacuum insulated container 40 as shown in Figure 4.
  • the container was cooled by spraying liquid nitrogen into the container and the temperature was controlled by a temperature controller 42 which regulated the flow of liquid nitrogen via a solenoid valve 43.
  • Liquid nitrogen was sprayed into the container near a small fan 44 located at the centre of the container 40.
  • the fan 44 was surrounded by a stainless steel screen (not shown) to avoid direct contact of liquid nitrogen with the columns to ensure even temperature distribution in the columns.
  • a vacuum of 10 ⁇ 3 torr was maintained between the inner and outer container during the experiment.
  • the top of the container was insulated with a 3.8 cm layer of styrofoam insulation.
  • Two detectors namely a thermal conductivity detector 50 and a flow proportional counting detector 27, were used to detect the hydrogen isotope species.
  • the thermal conductivity detector 50 detected H2, HD and D2 only, whereas the flow proportional counting detector 27 detected HT, DT and T2 for all the experiments because of the very low concentration of the tritiated species. Signals from the two detectors were recorded by a dual pen recorder and integrated by two integrators.
  • Liquid nitrogen was supplied by a 55 L container 25 connected to the solenoid valve 43 and the column container 40.
  • the temperature controller 42 was then set to the desired temperature. It usually took 1.5 to 2 hours to cool the column container 40 from room temperature to -140°C to -180°C.
  • the position of the six-way valve 20 was as shown in Figure 3(a).
  • the sample loop was evacuated by opening the valve leading to the vacuum pump.
  • the valve to the vacuum pump was closed and the loop was filled with the gas sample to the desired pressure by opening the valve on the sample cylinder 11 connected to the six-way valve 20.
  • the six-way valve 20 was switched so that the carrier gas passed through the sample loop 21 and flushed the sample through the column.
  • the column was cooled to as low as -186°C and the 2 L sample mixture was injected.
  • the He carrier gas was maintained at a flow rate of 4 L/min at a pressure of about 300 kPa measured just upstream of the column.
  • the column temperature was increased at a rate varying up to 10°C every 60 min to a final temperature near -150°C.
  • Selected results for experiments giving similar isotope separations are summarized in Table 1 compared with the results obtained at a constant temperature of -166°C. At -166°C, separation of all components was completed in about 330 min. There was overlapping of some of the components at this temperature, hence the sample would have to he partially recycled.
  • the net throughput was estimated to be about 270 mL/h or 135 mL/h/1 cm column.
  • the elution time was reduced to as low as 130 min corresponding to a net throughput of about 770 mL/h or 380 mL/h/1 cm column, which is more than five times the reported throughput of 50 to 75 mL/h/1 cm column reported by the Max Planck group.
  • Table 1 Selected Experimental Results for the 2 cm 7.5 m Column With Similar Isotope Separation for a Hydrogen Sample of 2 L Initial Temp. °C Rate of Temp. Change °C/h Final Temp.
  • the standard technique for dealing with separated hydrogen isotope species involves storage in a bed of a suitable powdered metal. Powdered uranium beds are commonly used in this regard, and the hydrogen species absorbed thereon are usually stored at room temperature. The ability to absorb hydrogen onto uranium powder also provides a means for separating the isotope species from the carrier gas which is not so absorbed.
  • the present invention includes the step of separating and storing such mixed dimers at low temperature free of catalyzing metals.
  • This feature of the invention takes advantage of the fact that hydrogen and its various isotopic species condense at about 20 K, while helium does not condense until about 4 K. Therefore, fractions eluted from the GC system in accordance with the invention may be separated from the helium carrier gas and captured for storage by cooling the effluent to abut 15 K.
  • the mixed species i.e. HD, DT and HT, may be captured and stored in pure form free from equilibration by using this technique.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Biochemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Procédé de séparation des différentes sortes d'isotopes d'hydrogène à partir de mélanges de ceux-ci, qui comprend : l'injection d'un certain volume de mélange d'isotopes dans une colonne de chromatographie en phase gazeuse à basse température, contenant à l'intérieur un tamis moléculaire comme matière de remplissage ; l'écoulement de ce mélange dans la colonne au moyen d'un gaz inerte sous pression qui n'est pas fortement absorbé par le tamis moléculaire dans les conditions d'écoulement dans la colonne ; et l'élution de la colonne des différentes sortes d'isotopes séparées,
       caractérisé en ce que l'injection initiale dans la colonne est faite, la colonne étant à une température dans la plage de -185° C à -170° C, et en ce qu'au cours de l'écoulement dans la colonne, la température de colonne est augmentée à une vitesse allant jusqu'à environ 10° C par heure jusqu'à une température maximale de colonne d'environ -145° C.
  2. Procédé selon la revendication 1, dans lequel le tamis moléculaire utilisé comme remplissage dans la colonne est un silico-aluminate de sodium ou de calcium.
  3. Procédé selon la revendication 2, dans lequel le tamis moléculaire utilisé comme remplissage dans la colonne est une matière de type 5A ayant une taille de pores d'environ 5 angstroems (0,5 nm).
  4. Procédé selon la revendication 1, 2, ou 3, dans lequel le tamis moléculaire utilisé comme remplissage dans la colonne est sous la forme de billes ayant des diamètres dans la plage de 0,25 à 0,42 mm.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le gaz support est l'hélium.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel la pression du gaz support est dans la plage de 100 à 800 kPa.
  7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel, à la suite de l'élution de la colonne, les différentes sortes d'isotopes séparées sont séparées du gaz support, dans le cas des isotopes H₂, D₂ et T₂ par absorption sur des lits d'uranium distincts, et dans le cas des isotopes HD, HT et DT par condensation à partir du gaz support à environ 15° K.
EP91120674A 1986-05-08 1987-03-30 Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène Expired - Lifetime EP0486070B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US06/861,336 US4732581A (en) 1986-05-08 1986-05-08 Gas chromatographic method for separating hydrogen isotopes
EP87302742A EP0245936B1 (fr) 1986-05-08 1987-03-30 Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène
US861336 2001-05-18

Related Parent Applications (1)

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EP87302742.9 Division 1987-03-30

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EP0486070A1 EP0486070A1 (fr) 1992-05-20
EP0486070B1 true EP0486070B1 (fr) 1994-11-09

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EP87302742A Expired - Lifetime EP0245936B1 (fr) 1986-05-08 1987-03-30 Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène
EP91120674A Expired - Lifetime EP0486070B1 (fr) 1986-05-08 1987-03-30 Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène

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EP87302742A Expired - Lifetime EP0245936B1 (fr) 1986-05-08 1987-03-30 Méthode chromatographique de gaz pour séparer des isotopes d'hydrogène

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US (1) US4732581A (fr)
EP (2) EP0245936B1 (fr)
JP (1) JPS6312329A (fr)
AT (2) ATE113861T1 (fr)
CA (1) CA1271142A (fr)
DE (2) DE3750751T2 (fr)

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US11185795B2 (en) 2012-07-06 2021-11-30 Waters Technologies Corporation Techniques for thermally insulating a chromatographic column
CN106693704B (zh) * 2017-02-15 2019-06-04 中国工程物理研究院材料研究所 一种置换色谱氢同位素富集分离方法
CN107051205B (zh) * 2017-02-15 2019-02-12 中国工程物理研究院材料研究所 一种低温钯置换分离方法
CN106693703B (zh) * 2017-02-15 2018-01-02 中国工程物理研究院材料研究所 一种置换色谱氢同位素分离装置
CN107930400A (zh) * 2017-12-07 2018-04-20 中国工程物理研究院核物理与化学研究所 一种氢氦分离与氢同位素浓缩耦合系统及方法
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CN112986447A (zh) * 2021-04-23 2021-06-18 中国原子能科学研究院 气相色谱分析装置
CN114544807B (zh) * 2022-02-15 2023-06-23 中国工程物理研究院材料研究所 一种氢同位素气体中杂质分析装置及方法

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EP0245936A3 (en) 1990-05-02
ATE107535T1 (de) 1994-07-15
EP0245936A2 (fr) 1987-11-19
DE3750100T2 (de) 1994-10-13
US4732581A (en) 1988-03-22
ATE113861T1 (de) 1994-11-15
JPS6312329A (ja) 1988-01-19
CA1271142A (fr) 1990-07-03
EP0245936B1 (fr) 1994-06-22
DE3750100D1 (de) 1994-07-28
DE3750751T2 (de) 1995-03-16
DE3750751D1 (de) 1994-12-15
EP0486070A1 (fr) 1992-05-20
JPH0412167B2 (fr) 1992-03-03

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